Meta-phenylphenoxy substituted siloxanes and process therefor



Patented Nov. 21, 1967 United States Patent ()flfice 3,3543% intermediate product with the dihydroxy-substituted aro- 3 354 194 matic-compound or in the first step, the silane or siloxane META-PHENYLPHENdXY SUBSTITUTED SILOX- material can be reacted with the dihydroXy-substituted H ANE AND PROCESS THEREFQR aromatic compound and the resulting intermediate product erbert C. Kaufman, New Haven, Conn., assignor to Ohn h fi 1 Mathieson Chemical Corporation a corporation of 5 can nt e na step, be reacted with meta-phenoxy phenol. Virginia Dihalosilanes of the formula: No Drawing. Filed Jan. 30, 1964, Ser. No. 341,425 R 15 Claims. (Cl. 260-4483) X-si-X I R ABSTRACT OF THE DISCLOSURE wherein X is a halogen selected from the group consisting Meta-phenoxy phenol is reacted with a dialkyl or diaryl of chlorine, bromine OI iodine and R is alkyl Of from 1 t0 dihalosilane or disiloxane to form an intermediate product 5 carbon atoms or aryl of not more than 8 carbon atoms, which in the second stage of the reaction is reacted with are suitable starting materials in the process of this invena dihydroxy-substituted aromatic compound, such as retion. Examples of such silanes include dimethyldichlorosorcinol, to yield a high temperature resistant, silicon- Silime, di-H-PTOpyldichlofosilane, diamyldichlofosilane, containing fluid composition. If desired, the silane or phenyldichlorosilane, etc. and the corresponding bromine siloxane can be first reacted with the dihydroXy-substituted and iodine derivatives. aromatic compound and the resulting intermediate product DihalosilOXancs Suitable as starting materials in this can, in the final step, be reacted with meta-phenoxy phenol. novel process have the formula:

' i" F The invention relates to novel silicon-containing com- XSiOSi-X positions which are prepared by reacting a dihalosilane or a dihalodisiloxane with meta-phenoxy phenol to form an intermediate product which is then reacted with a dihywhere R is alkyl of from 1 to 5 carbon atoms or aryl of droxysubstituted aromatic material to yield products havnot more than 8 carbon atoms and X is chlorine, bromine ing repeating disiloxanyl-meta-phenoxy linkages. or iodine. Typical examples of useful siloxanes include The silicon-containing compositions of this invention in- 1,3-dichlorotetramethylsiloxane, 1,3-dichlorotetraethyls elude compounds of the formula:

loxane, 1,3-dichlorotetraisoamylsiloxane, 1,3-dichlorote and of the formula: ratolylsiloxane, etc. and the corresponding bromine and l l iodine derivatives.

I Useful dihydroXy-substituted aromatic compounds in- I i R n i clude those of the formula: 0- 0s o 0 U I L I U Q 4 OH R R wherein R and R are each selected from the group consisting of alkyl of from 1 to 5 carbon atoms and aryl of OH not more than 8 carbon atoms, R" is selected from the Where is hydrogen but may be alkyl of from 1 to 5 group Consisting of hydrogen alkyl of from 1 to 5 carbon carbon atoms or aryl of not more than 8 carbon atoms atoms, phenyl and alkaryl of not more than 8 carbon and where the hydroxyl groups may be ortho, meta, or

atoms, and n 15 an.1ntege1' of from 0 to about para to each other but where resorcinol is preferred. Rethe Prawnt thfire are a R of mammals sorcinol, hydroquinone, dihydroxytoluene, dihydroxybiwhich approach the high degree of oxrdatrve, thermal and phenol and catechol represent useful dihydmxy hydrolytic stability as well as the high degree of lubricity I a q for lubricants and hydraulic fluids used in high Preferably the reaction is carried out in the presence of speed alrcraft. However, these compounds of the prior art inert Solvent which can be for example decalin diox do not eXhibit good low-temperature characteristics and ane, benzene, toluene and Xylene. The temperature (overh i ViSCOSitieS decrease rapidly with temperature all) of the reaction can be varied from about 0 C. to creases. 0

The product of the instant invention satisfactorily meets ZRE Z E Sg ZP upon the partlcular reactlqn con an Tequimments f0? Such lubricants and hydraulic fluids- It has been found convenient to carry out the reaction of The C m iHa ll f meta-linked P y ethefs and SilOX- this process at reflux temperature although lower temperane or silane results in hydrolytically stable fluids exatures can be employed if desired. The amount of the hibiting pour points down to -40 F. or below. silane compound employed can vary from about 1.5 to

The two-stage reaction of this invention is conducted about 4.0 moles per mole of dihydroxy aromatic comby first reacting meta-phenoxy phenol with the dihalopound utilized and preferably will be not less than about silane or dihalosiloxane, and then reacting thus-formed 1.0 mole per mole of meta-pheuoxy phenol employed The tive.

Found: 720.

time of the overall reaction will vary widely and generally will range from about 12 to, about 96 hours or more. Although the process of this invention can be advantageously operated at atmospheric pressure, subatomospheric pre'ssures as well as pressures up to about seven atmospheres or more can be utilized.

5-liter, glass, round-bottomed reactor equippedfwitha "-A jacketed addition funnel, cooled by circulating ice The products of this invention can be conveniently recovered from the reaction mixture by distillation or by other methods well known in the art.

The compounds of this invention are useful as lubricants, hydraulic fluids, heat transfer media, transformer oils, etc. i

The following examples are illustrative and not limita- Example I To a reaction flask equipped with a Dry Ice condenser I there was charged 0.15 mole of 1,3-dichlorotettamethyl disiloxane in 100 g. of Decalin at ambient conditions. To

the mixture was rapidly added 0.15 mole of meta phenoxyphenol with stirring. The Dry Ice condenser prevented the escape of the volatile reactant with the evolving hydrogen chloride. The hydrogen chloride evolution began ly evolved and, after one hour, all the resorcinol had dissolved. The temperature of the mixture was raised to the reflux temperature of the Decalin, viz. 194 C., and maintained at that temperature for 12 hours.

The resulting amber-colored solution was cooled and distilled to remove the Decalin and unreacted phenols.

Further distillation yielded products having the general formula shown below:

CH3 C 3 Product A: Sym-tetrametbyl bis (meta-phenoxyphenoxy) disiloxane. Formula: See general formula above where n=0. Weight recovered: g.distilled as a colorless liquid at 2258 C. (0.7 mm. Hg).

.Analysis.--Calcd. for C H Si O Si, 11.16%. Found:

j Si, 11.1%.

Molecular Weight-Calcd. for C H Si O 502. Found: 485.

. Product B: Sym-bis (tetr amethyl, meta-phenoxy phenoxydisiloxanyl) meta-benzene. Formula: See general formula above where n=1. Weight recovered: 10 g.-

distilled as a pale yellow liquid at 278280 C. (0.07 mm.

Analysis.-Calcd. for c rn sno Si, 15.09%. Found: Si, 15.20%.

Molecular WeightCalcd. for C H Si O 742.

Example 11 To an apparatus similar to that of ExampleI there was 7 charged 0.50 mole of resorcinol and 1.00 mole of'water dissolved in 300 ml. of dioxane. The reaction flask was a ta. ta.

water andprotected from the atmosphere'by a drying f tube, was also connected to the reactor. A slow stream of nitrogen was introduced over the reactants. 2.00 moles of-dimethyldichlorosilane were added to the reaction mixture with no visible sign of reaction. The temperature was raised to 36 and hydrogen chloride began to evolve slowly. When a temperature of 71 'C. was reached, the dirnethyldichlorosilane began to reflux and hydrogen chloride w-ascopiously evolved. After 24 hours the tempertature was raised to 103 C. and the reaction mixture was refluxed for another 24 hours. After the contents of the reactor had been cooled, 1.10 moles of meta-phenoxy phenol was added. As the temperature was raised to reflux at 103 C. hydrogen chloride began to be evolved.

' After 24 hours the evolution of hydrogen chloride had ceased and the contents of the flask were cooled and stripped of dioxane and unreacted phenols.

Further distillation yielded the following four products:

Product A-Weight g.; distilledat 180 C./0.08 mm. Hg. By analysis this fraction was shown to be dimethyl bis (m-phenoxy phenoxy) silane.

Product BWeight g.; distilled at 2236 C./0.08 mm. Hg. This product was sym-tetramethyl bis (metaphenoxyphenoxy) disiloxane.

Product C Weight 120 g.; distilled at 275278 C./ 0.06 mm. Hg. This product was sym-bis (tetramethyl, meta-phenoxy-phenoxydisiloxanyl) meta-benzene.

Product DWeight 30 g.; could not be distilled. Product D is an exemplification of a product of the formula:

where n is greater than 1.

ExampleIII f The procedure and reactants of Example II were used in this example except that diphenyldichlorosilane was substituted for the dimethyldichlorosilane of Example II. The major product was sym-bis (meta-phenoxyphenoxy, diphenyl) meta-disiloxybenzene of the formula:

Product E a white crystalline monomer having a melting point. of

107 C. and a boiling point of 315 C. (0.7 mm. Hg) WhlCh was recovered in 40 percent yield. The balance was a resinous polymer. The resinous polymer'formed had the formula:

The flash point of Fraction B was found to be 480 F., the fire point 555 F. and the spontaneous ignition where n is greater than 1.

Product E was analyzed for silicon, carbon and hydrogen and the following results were obtained:

Analysis.--Calcd. for C H Si O Si, 6.65; C, 77.02; H, 5.00. Found: Si 6.6, 6.6; C, 77.10, 76.98; H, 4.97, 4.95.

Example IV In this example 1.0 mole of diphenyldichlorosilane was reacted with 0.5 mole of resorcinol in a mixture of dioxane and benzene and refluxed at 95 C. until hydrogen chloride evolution ceased. The solvents were stripped off under vacuum and 0.62 mole of meta-pheuoxy phenol was added. The reaction mixture was brought to reflux at 295 C. and maintained at that temperature for 24 hours until the evolution of hydrogen chloride ceased. Excess phenols were stripped oil and on continued distillation the product sym-bis (meta-phenoxyphenoxy, diphenyl) meta-disiloxybenzene (B.P. 315 C. at 0.7 mm. Hg) was recovered in 40 percent yield, the residue resinifying. The formula of the resinified residue was as foltest value was 1100 F. The table below lists the results obtained in certain viscosity tests made with the three products of Example I.

VISCOSITY MEASUREMENTS Sample F. 100 13. cs. 210 F. es. 500 F. cs.

Product A--. Pour (int... 22. 0 4.3 0. Product B 32.4 5.8 1&3 Product 0 do 95. 0 23.0 3. 92

What is claimed is: 1 1. A method for preparing silicon-containingcompounds which comprises: (A) reacting a material selected frolrln the group consisting of .a dihalosilaue of the form a:

awaaiw where n is greater than 1. i

Recrystallization of the product from cold isopropanol gave a white crystalline solid, M.P. 107 C.

Using the procedure of Military Specification H-8446 the hydrolytic stability of Product B of Example I was determined. Seventy-five grams of the product together with 25 g. of water and a bright copper strip specimen were placed in a glass bottle and rotated end-over end at 200 F. for 48 hours. The copper strip specimen, which exhibited a weight loss of 0.22 mg./crn. was bright and untarnished at the conclusion of the test. Before and after the test the acid number of the silicon-containing fluid (Product B) was zero. The acid number of the water layer was measured and found to be 3.89 mg. KOH/g. at the end of the test as compared to 3.45 mg. KOH/g. at the start. Thus the increase in acid number was 0.44 mg. KOH/g. while the maximum allowable for a hy draulic fluid is 5.0 mg. KOH/ g. The viscosity of the silicon-containing fluid (at 100 F.) as measured before the test was 32.4 cs. while the viscosity (at 100 F.) at the conclusion of the test was 32.6 cs.

where X is a halogen selected from the group consisting of chlorine, bromine and iodine, and R' is selected from the group consisting of alkyl of from 1 to 5 carbon atoms, phenyl and alkaryl of not more than 8 carbon atoms, with a compound of the formula:

wherein R" is selected from the group consisting of hydrogen, alkyl of 1 to 5 inclusive carbon atoms, phenyl and alkaryl of not more than 8 carbon atoms to form an 7 intermediate product, and (B) reacting said intermediate product with meta-phenoxy phenol, "there being from about 1.5 to about 4.0 moles of the said material reacted with each mole of the said compound and there being not less than about 1.0 mole of the said material reacted per mole of meta-phenoxy phenol.

2. The method of claim 1 wherein the said material is a dihalosilane.

3. The method of claim 1 wherein the said material is a dihalodisiloxane.

4. The method of claim 1 wherein the said material is l,3-dichlorotetramethyldisiloxane.

5. The method of claim 1 wherein the said material is dimethyldichlorosilane.

6. The method of claim 1 wherein the said material is diphenyldichlorosilane.

7. The method of claim 1 wherein the said compound is resorcinol.

8. The method of claim 1 wherein the reaction temperature is from about C. to about 300 C.

9. The method of claim-1 wherein the reactions are carried out in the presence of an inert solvent.

10. The method of claim 1 wherein the said material is 1,3-dich1orotetramethyldi.siloxane and the said compound is resorcinol.

11. The method of claim 1 wherein the said material is dimethyldichlorosilane and the said compound is resorcinol.

12..The method of claim 1 wherein the said material is diphenyldichlorosilane and the said compound 'is resorcinol.

13. A silicon-containing compound selected from the class consisting of compounds of the formula:

and of the formula:

Q Q t a. Q Q

wherein R and R are each selected from the group consisting of alkyl of from 1 to 5 carbon atoms, phenyl and alkaryl of not more than 8 carbon atoms, R is selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms, phenyl and alkaryl of not more than 8 carbon atoms, and n is an integer from 1 to about 10.

CH1 CH3 CH3 CH;

References Cited UNITED STATES PATENTS 3,125,634 3/1964: Murray et a1. 260448.8 X 3,125,635 3/1964 Murray et a1. 260-448.8 X

3,277,136 10 1966 Thiessc 260448.8

roBIAs ELEVOW, Primary Examiner. HELEN M. MCCARTHY, Examiner. P. F. SHAVER, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,354,194 November 21, 1967 Herbert C. Kaufman It is hereby certified that error appears in the above numbered pat ent requiring correction and that the said Letters Patent should read as. corrected below.

Column 1, lines 31 to 40 and column 7, lines 51 to 6D, for that portion of each formula reading same column 1, lines 42 to 48, the formula should appear as shown below instead of as in the patent:

F @OQO-Si o O-ISi ego-Q A R n Signed and sealed this llth day of February 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A METHOD FOR PREPARING SILICON-CONTAINING COMPOUNDS WHICH COMPRISES: (A) REACTING A MATERIAL SELECTED FROM THE GROUP CONSISTING OF A DIHALOSILANE OF THE FORMULA:
 13. A SILICON-CONTAINING COMPOUND SELECTD FROM THE CLASS CONSISTING OF COMPOUNDS OF THE FORMULA: 